Azo dyestuffs



, a -NH.CO-- bridge, R stands for a mononuclear or 2,824,093 Patented Feb. 18, 1958 atent a COOH group in ortho-position to the azo bridge, and,

2,824,093 on the other hand, with one mol of a 1-aminoanthra- A10 S UFFS quinone-Z-sulfonic acid of the formula Jakob Benz, Base], and Walter Wehrli, Riehen, Switzer- 5 land, assignors, by mesne assignments, to Saul & Co., 0 Newark, N. J., as nominee of Fidelity Union Trust Company, executive trustee under Sandoz Trust 8 SoaH 7 No Drawing. Application September 28, 1953 A Serial No. 382,834 10 6 5 Claims priority, application Switzerland October 3, 1952 (b) 8 Claims. (Cl. 260-146) The present invention relates to substantive azo dyewherein R and R" have the previously-indicated sigstuffs which correspond to the formula nificances and nucleus A may be substituted as previously (H) NH:

7 8 303B 2 A A 6 5 H 111 N=C-CH2 0 NHR-NHR"C\ C-NH-Rr-N\ O-a a-OC wherein each a stands for a hydrogen atom or the 2a's set forth and then treating the resultant azo dyestutf, together represent Cu--, w stands for a hydrogen or wherein if desired a third halogen atom of the triazine chlorine atom or a sulfonic acid, sulfonic acid amide ring may be replaced by -OH, NH or the radical Substituted Sulfollic acid amide p, 2 Stands for of an amine, with a copper-yielding agent, the treatment L- z the residue of an amine, 1 Stands being carried out with the dyestufi in substance or on for a mononuclear radical of the benzene series or a the fib binuclear radical of the benzene series wherein the two Alternatively one mol of the triazine compound may benzene nuclei are linked together by a be condensed in any desired order of succession with one mol of a 1-aminoanthraquinone-Z-sulfonic acid (b) and 40 binuclear radical of the benzene series, R stands for with 1 mol of watepsoluble Signalman: of the formula a simple bond or a residue of the formula Ha OC=N U 1 yam,

which may be further substituted in the benzene nucleus (c) by methyl or methoxy, and wherein the nucleus A may be monosubstituted by -SO H in one of the 5-, 6-, 7- or PF monosu'bstimled by infme of wherein R; has the precedingly-recited significance, couthe 6- or 7-pos1t10ns, or disubstituted by chlorme in both pling the resultant condensation product with one mol i qg b d t E b of the diazo compound of an amine of the benzene series g gg g l g ggi fia gg g f :2: containing COOH group in ortho-position to the amino group and then treating the resultant azo dyestutf, in which in the presence of an acid-binding agent, one mol of a triazine compound, which contains at least two and at If desued a third halogen atom of the mazme nng may most three replaceable halogen atoms connected to carbon replaced by T T the radical an amine atoms, in any desired order of succession, on the one Wlth a copperyleldmg agent, the dyestufi belflg treated hand with one f a water so1ub1e and, if desired, in substance or on the fiber. The last-mentioned replacecoppered, aminomonoazo compound which in the unmeflt y, if desired, be carried out before collPling the coppered state corresponds to the formula condensation product with the diazotized amine.

' In the aminomonoazo compounds of the formula a,

HrC-C=N employed in preparing the azo dyestuffs of the present pp 55 invention, according to the first described process embodi- BPN=N HC C ment, the symbol R represents a phenyl. radical, a stil- (a) benyl radical, or a benzoylaminophenyl radical, which radicals is the stilbenyl radical, the presence of which in wherein R has the previously-indicated significance, and the y molecule imparts P t y good P p R; stands for a radical of the benzene series containing tie to the product. Possible subsutuents for the phenyl radicals may be further substituted. The preferred R the individual components.

azine, etc.

and benzoylaminophenyl radicals are preferably halogen atoms (for example chlorine), alkyl radicals (for example methyl), alkoxy radicals (for example methoxy, ethoxy, etc.) sulfonic acid groups and sulfonic acid amide groups which may be alkylated, cycloalkylated, aralkylated or arylated at the nitrogen, while preferred substituents for the stilbenyl radical are sulfonic acid groups. R moieties are the Z-aminobenzene-l-carboxylic acid moieties and derivatives thereof substituted by halogen (for example chlorine), alkoxy (for example methoxy, ethoxy, etc.), or acylamino (for example acetyl amino). Preferred representatives of this series are also the 1-carboxy-2-aminobenzene-4- and --sulfonic acids and sulfonic acid amides. The latter may be substituted at the nitrogen atoms of the sulfonic acid amide groups, for example by alkyl, cycloalkyl, aralkyl or aryl; especially preferred in this connection are the methylamides, 2'-hydroxyethylamides and 2'-carboxyphenylamides.

The aminomonoazo compounds of the formula 11 are prepared by coupling the diazotized Z-aminohenzenelcarboxylic acids with the 1 (amino) pheny1- or 1 (aminobenzoylamino) -phenylor l-(4"-amino)-stilbenyl-(4')-3-methyl-5-pyrazolones in advantageously neutral or weakly acid medium.

The aminopyrazolones and Z-aminobenzene-l-carboxylic acids, employed for the second process embodiment of the invention, are preferably the same as those described for the preparation of the aminomonoazo compounds (a) required for carrying out the first process embodiment of the invention. The coupling of the diazo compounds with the secondary .or tertiary condensation products is here advantageously carried out in neutral or alkaline medium.

The l-aminoanthraquinone-Z-sulfonic acids of formula b which are employed in both aforedescribed process embodiments are obtained by the condensation of l-amino- 4-halogenanthraquinone 2 sulfonic acids with diaminobenzenes, diaminodiphenyls, diaminobenzovlaminobenzenes and diaminobenzoylaminodiphenyls, which diamino compounds may advantageously be substituted by alkyl, alkoxy, carboxy or sulfo groups. The last two enumerated compound types (diarninobenzoylaminobenzenes and diaminobenzoylaminodiphenyls) can also be pre-.

pared by treating the condensation products of l-amino- 4-halogenanthraquinone-Z-sulfonicacids and diaminobenzenes or diaminodiphenyls with nitrobenzoyl halides, followed by reduction of the nitro group to the amino group. The condensation of 1-amino-4-halogenanthraquinone-Z- sulfonic acids can also be carried out with compounds of the benzene or diphenyl series which contain only 1-aminoanthraquinone-Z-sulfonic acids (.5) are used as free acids or in the form of their salts. Technical mixtures, such for example as the 2,5- and 2,8-disulfonic acid mixture or the 2,6- and2,7disulfonic acid mixture, can be used as such, without preliminary separation into Triazine compounds withat least two and at most three replaceable halogen atoms connected to carbon atoms,

and which are particularly suitable for the preparation of a monoazo dyestutf of the present invention, coml-methyl.-3,S-dichlorotriazine, l-phenyl 3,5 dichlorotri prise, for example, cyanur'ic chloride, cyanuric' bromide,

The condensation of amines with triazine compounds containing replaceable halogen atoms is known. It is known that the preparation of the primary condensation product, i. e. the replacement of the first halogen atom by the radical of an amine, proceeds readily. For this reason, this phase is carried out at about 0 C. The substitution of the second halogen atom by the radical of an amine requires a somewhat higher reaction tem-. perature, for example 30-50 C., while the replacement of the third halogen atom which may be present can he carried out only at elevated temperature, for example at -100" C., and with a readily reacting amine. Such readily reacting amines are for example aminobenzene, 1 amino 4 acetylaminobenzene, N methylaminobenzene, methylamine and monoethanolamine. The said third halogen atom can also be replaced by hydroxy or by amino.

The uncoppered dyestuffs of the present invention dye cotton and fibers of regenerated cellulose in pure green shades. They contain, in the pyrazolone-azo moiety, a metallizable group which can be coppered on the fiber by a single bath processor by an after-coppering process. The coppered dyeings are characterized by good fastness to light. to washing and to perspiration.

The dvestufis can also be coppered in substance. This coppering is carried out according to any one of the various methods known from the literature, for example by heating the dvestuff with a copper salt in a weakly acid to alkaline medium, if desired with the use of pressure and/or in the presence of amm nia or of an organic base such as diethan lamine. p ridine. mouinoline. or in a melt of an a kali salt of a low molecular aliphatic m carh x c acid.

The metalli ed azo dvesfnfr's dve cotton and fibers of re enerated ellu e in. simil r shade as the un onered d estuffs. The dyeings are fast to light. to washingand to ers irati n.

The dvein s of pr ctically all the uncnnpered and met llized dv stnifs of the present inventi n can als he treated with cati nmctive cop er c m ex com ounds, which ma be basic (such as are obtaina le according to Swiss Pa en s Nos. 253.709 and 2610 8-052), wherebv enhanced fastness pro erties, particularlv as regards ligh+- washand persniration-fastness. are btained.

The following examples are illustrative of the invention. In these examples, the parts are parts by weight, the percentages are by weight and the temperatures are in degrees centigrade. The preparation of the respective intermediate is known from the literature.

EXAMPLE 1 A neutral solution of 67.9 parts of the aminomonoazo compound, obtainable by coupling diazotized l-carboxy-Z- aminobenzene-S-sulfonic acid with l-[4"-amino-l',l"- stilbenyl (4')]-3-methyl-5-pyrazolone-2',2" disulfonic acid, in 1000 parts of water is added at O-3 in the course of 30 minutes to a suspension of 18.4 parts of cyanuric chloride in 300 parts of ice water. The resultant mass is stirred for one hour at 0-3", care being taken by the dropwise addition of dilute aqueous sodium carbonate solution that the condensation mixture constantly hasa weakly acid reaction. Thereupon a neutral solution of 40.9 parts of l-amino-4-(4'-amino)-phenylaminoanthraquinone-Z-sulfonicacid in 800 parts of water are added dropwise to the monocondensation product. The temperature of the mass is then raised to 40-45 and stirring carried out at this temperature for two hours, the reaction of the mixture being maintained weakly acid throughout by the addition of dilute aqueous sodium carbonate solution. After the addition of 18 parts of aminobenzene, the

H 2,824,093 a a 5 a 6 reaction mass is heated for one hour to 90-95. The fonate in 800 parts of water are added at -3" to a susnow-present tertiary condensation product is then salted pension of 18.4 parts of cyanuric chloride in 300 parts of out, filtered, and dried. It corresponds to the formula ice water. The mixture is stirred for two hours at this 801E NHCCHB I 151 \IIT /N=C-OH3 N A CCH-N=N Hots and dyes cotton and fibers of regenerated cellulose in temperature and, during this operation, a dilute aqueous green shades, the fastness properties of which are consodium carbonate solution is added dropwise at such a siderably improved by treatment with copper-yielding rate that the reaction mixture is constantly weakly acid. agents. Thereupon a neutral solution of 67.8 parts: of the amino- The dyestulf can be coppered in substance. To this monoazo compound, obtained by coupling diazotized 1- end, it is suspended in 1000 parts of water at 85, and to carboxy-Z-aminobenzene-S-sulfonic acid amide with 1- the suspension there is gradually added a solution of 25 [4-amino-1,l-stilbenyl-(4)l-3-methyl 5 pyrazo1oneparts of crystalline copper sulfate, 40 parts of a 2,2"-disulfonic acid, in 500 parts of water are added aqueous ammonium hydroxide solution and 100 parts of dropwise to the monocondensation product. The temwater. The mixture is maintained at 9095 for 30 perature of the mass is then raised to -40 in the course minutes and, upon completion of the ensuing coppering, of one hour, during which time care is taken that the the dyestuff is isolated. It corresponds to the formula reaction remains weakly acid by the dropwise addition of ("J NH;

SOsH lfHCnHs N \N N=C-CHs I II I 0 NH HN-C\ -NH CH=CH N\ r N l l c=oN=N -c6-oo The green dyeing produced on cellulose fibers with this dilute sodium carbonate solution. The mixture is then pp complex compound are Characterized y y 55 stirred for some additional time at 40, after which 18 good fastness F light: to Washing and to Perspirationparts of aminobenzene are added thereto and the tem- EXAMPLE 2 perature then maintained at -95 for one hour. The

A solution of 60.9 parts of sodium l-amino-4-[4'-(4"- so-obtained tertiary condensation is salted out, filtered and amino)-phenyl]-phenylaminoanthraquinone-2,3" disuldried. It corresponds to the formula l N i A O Q H I l C SOzH SO;H

' and dyes cotton and fibers of regenerated cellulose in green shades the fastness properties of which are improved by treatment with copper-yielding agents.

The preparation of the copper complex compound in substance may be carried out, for example according to the process set forth in Example 1. Such copper complex compound corresponds to the formula SOaH NHCsHs 80 H I fi 0 W QHM am EXAMPLE 3 The cupriferous monoazo dyestutf described in Example 1 is also obtained when, in lieu of the 67.9 parts of the aminomonoazo compound of Example 1, use is made of the corresponding quantity of copper complex thereof, obtained for instance by coppering the aminomonoazo compound with copper sulfate in an aqueous solution containing sodium acetate.

The copper complexcompound is dissolved in 1008 parts of water in the presence of 5 parts of lithium carbonate and parts of sodium carbonate. The solution is then added dropwise to a suspension of 18.4 parts of cyanuric chloride and 300 parts of Water. The tempera-- ture of the condensation mass is held at 03; the reaction mixture is maintained weakly acid throughout by the dropwise addition of dilute lithium carbonate solution. The so-obtained monocondensation product is reacted, after the manner described in Example 1, with, 40.9 parts of 1-amino-4-(4'-amino)-phenylarninoanthraquinone-Z- sulfonic acid, after which the resultant secondary condensation product is reacted with 18 parts of aminobenzene. The produced tertiary condensation product is precipitated from the hot condensation solution by the addition of potassium carbonate and a small quantity of potassium chloride, after which it is filtered hot, washed with 5% aqueous sodium chloride solution and finally dried.

The identical cupriferous monoazo dyestuif is obtained when first the anthraquinone derivative, then the copper complex of the aminomonoazo compound, and finally the aminooenzene are reacted with cyanuric chloride.

EXAMPLE 4 The uncoppered monoazo dyestuif described in ample 1 can also be prepared by reacting an aqueous solution of 49.5 parts of the disodium salt of l-[4-amino- 1,1" stilbenyl (4')] 3 methyl 5 pyrazolone 2',2 disulfonic acid with an aqueous suspension of 18.4 parts CH=CHON Q I 8 of cyanuric chloride according to the dataset forth in Example 1, followedby condensation of the primary condensation product with 40.9 parts of 1-amino-4-(4-amino)-phenylaminoanthraquinone-Z-sulfonic acid and reaction of the secondary condensation product with 18 parts of aminobenzene. The tertiary condensation product is coupled at 0-5 in a. medium rendered alkaline with so- -cE-o c- SOaH SOaH HIN 01S dium carbonate, with the diazo compound of 21.7 parts of 1-carboxy-2-aminobenzene-S-sulfonic acid. The identical monoazo dyestufi? is obtained when the 18.4 parts of cyanuric chloride are first condensed with 40.9 parts of 1-amino-4-(4'amino)-phenylaminoanthraquinone-2-sulfonic acid, then with 49.5 parts of 1-[4"-amino- 1',1" stilbenyl (4')] 3 methyl 5 pyrazolone 2', 2 disulfonic acid and finally with 18 parts of aminobenzene, and then the resultant tertiary condensation product coupled with the diazo compound of 21.7 parts of 1-carboxy-2-aminobenzene-5-sulfonic acid.

The two modes of procedure set forth in the preceding two paragraphs can be modified in that the diazotized 1- carboxy-Z-aminobenzene-S-sulfonic acid is not coupled with the tertiary condensation product, but rather--in similar manner-coupled with the secondary condensation product and the conversion of the latter into the tertiary condensation product only thereafter carried out.

Theuncoppered monoazo dyestufr obtained according to the foregoing methods can be coppered in substance or on the fiber.

The following tables set forth further azo dyestuffs which can be prepared according to the processes described in Examples 14. All these .azo dyestuffs correspond to the formula Tables I-III set forth the amides corresponding to the substituents X, Y and Z. In Table IV the symbols X and Y also indicate the corresponding amines; however, in this table, the symbol Z designates the substituent itself.

All the azo dyestuffs of the tables dye cotton and fibers of regenerated cellulose in green shades with very good fastness to light, to washing and to perspiration.

a 13 EXAMPLE 55 1 part of the uncoppered monoazo dyestuff prepared according to Example 1 is dissolved in 200 parts of water at 100. This solution is poured into 3400 parts of water, 50 parts of anhydrous sodium sulfate are added, and then 125 parts of prewetted cotton material are entered at -30". The bath is heated to 9095 and maintained at this temperature for minutes. Thereupon it is allowed to boil for 15 minutes and then to cool down to 75. The dyed material is then rinsed and dried.

The thus-treated dyed cotton is, for after treatment purposes, introduced into a bath consisting of 2500 parts of water, 3.75 parts of crystalline copper sulfate and 3.75 parts of acetic acid, and the material treated in the said bath at 60 for 20 minutes. The material is then rinsed and dried.

EXAMPLE 56 1 part of the coppered dyestuff obtained according to paragraph 2 of Example 1 is dissolved in 200 parts of water at 100. This solution is poured into 3400 parts of water, parts of anhydrous sodium sulfate are added, and 110 parts of pre-wetted cotton or viscose yarn are entered at 20-30". The bath is warmed to 93 and the material thoroughly moved around therein for 30 minutes. The oath is then allowed to cool to 70, and the material rinsed and dried.

EXAMPLE 57 The dyeings obtained according to Examples and 56 may also be after treated as follows: The rinsed dyeing is manipulated for 30 minutes at 60-70 in a bath consisting of 3000 parts of water and 3 parts of a cupriferous condensation product built up on the basis of dicyandiamide, after which the coppered dyeing is rinsed and dried.

SOzH NH-t and methoxy; w stands for a member selected from the group consisting of H, Cl, -S0 H, and sulfonic acid amide, sulfonic acid morpholide, N-lower alkyl sulfonic acid amide, N-lower hydroxyalkyl sulfonic acid amide,

5 N-cycloalkyl sulfonic acid amide, N-aralkyl sulfonic acid amide and N-aryl sulfonic acid amide groups; z stands for a member selected from the group consisting of Cl, OH, NH;, lower alkylamino, lower hydroxyalkylamino, mononuclear carbocyclic arylamino and monoaminomonoazobenzene radicals; R stands for a member selected from the group consisting of mononuclear radicals of the benzene series and binuclear radicals of the henzene series wherein the two benzene nuclei are linked together by a bridge selected from the group consisting of -CH=CH and -NH.CO, each of the last-mentioned two benzene nuclei containing a sulfonic acid group in ortho-position to the said bridge when the latter is -CH=CH; R standsfor a member selected from the group consisting of mononuclear and binuclear radicals of the benzene series; and R" is a member selected from the group consisting of the l-aminoanthraquinone- Z-sulfonic acid group, the 1-aminoanthraquinone-2,5-disulfonic acid group, the 1-aminoanthraquinone-2,6-disulfonic acid group, the l-aminoanthraquinone-2,7-disulfonic wherein u stands for a member selected from the group consisting of hydrogen, sulfonic acid and sulfonic acid Having thus disclosed the invention, what is claimed is: 55 amide; b stands for a member selected from the group 1. A member selected from the group consisting of azo dyestufis which correspond to the formula consisting of hydrogen and sulfonic acid; I stands for a member selected from the group consisting of phenyl and and complex copper compounds thereof, wherein n stands for one of the numerals 1 and 2; v stands for a member methyl, and R stands for a member selected from the group consisting of a mononuclear and a binuclear radiselected from the group consisting of hydrogen, methyl cal of the benzene series.

3. Ap a z o dyestufl which corresponds to the formula wherein u stands for a member selected from the group consisting of hydrogem'sulfonic acid and sulfonic acid amide; b stands for a member selected from the group consisting of hydrogen and sulfonic acid; t stands for a member selected from the group consisting of phenyl and methyl, and R stands for a member selected from the group consisting of a mononuclear and a binuclear radical of the benzene series.

4. The azo dyestufi which corresponds to the formula 801E NHCoHs NnGHN-b l-NH crr=cn N N C=C---N=N $01K SOIH z 5. The azo dyestufi which corresponds to the formula SOaH IITHCaHu o Nil-Q Him- C-NH cn=on N 80:11 SOZH L c,

GuOF HgNOzS 6. The azo dyestuff which corresponds to the formula 17 7. The azo dyestufi which corresponds to the formula NHCIHI SOl SOQH

8. The azo dyestufi which corresponds to the formula NHCHI References Cited in the file of this patent UNITED STATES PATENTS UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,824.,093 February 18, 1958 Jakob Benz et a1.

It is hereb certified that error appears in the printed specification of the above num cred patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 70, for radicals read -radical--; column 5, line 54, for dyeing read dyeings; columns 5 and 6, formula at bottom of page,

right-hand portion thereof, should appear as shown below instead of as in the patent:

HOOC

' HQNOI Signed and sealed this 10th day of June 1958.

[SEAL] Attest KARL H. AXLINE,

Oomflnim'oiwr of Patents. 

1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF AZO DYESTUFFS WHICH CORRESPOND TO THE FORMULA 